Trends in Conjugated Chalcogenophenes: A Theoretical Study.
Trends in Conjugated Chalcogenophenes: A Theoretical Study.
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DOI：
10.1002/chem.202100270
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发表时间：
2021-05
期刊：
影响因子：
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通讯作者：
Valentina Topolskaia;Adam A. Pollit;Susan Cheng;D. Seferos
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文献类型：
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作者：
Valentina Topolskaia;Adam A. Pollit;Susan Cheng;D. Seferos
重原子取代在硫代酚是一个通用的策略，以调整和最终改善共轭聚合物的性质。虽然噻吩单体通常在聚合物设计中实现，但相对较少的是关于较重的硫基吩的分子性质。在此，我们使用密度泛函理论（DFT）计算来研究16族杂原子（包括放射性钋）如何影响多硫基烯的性质，包括键长、链扭、芳香性和光学性质。较重的硫代酚在性质上更似抛物线，因此具有较小的带隙和较大的平面度。我们同时考虑中性和自由基阳离子。p型掺杂后，键长重排表明电子结构更加离域，结合光学计算与共轭聚合物链上电荷存储的极化子模型相一致。在分子水平上更好地理解这些材料的性质，将不可避免地对材料设计有用，因为聚合物界继续探索更多的主要群体包含聚合物来解决电子设备中的问题。
Heavy atom substitution in chalcogenophenes is a versatile strategy for tailoring and ultimately improving conjugated polymer properties. While thiophene monomers are commonly implemented in polymer designs, relatively little is known regarding the molecular properties of the heavier chalcogenophenes. Herein, we use density functional theory (DFT) calculations to examine how group 16 heteroatoms, including the radioactive polonium, affect polychalcogenophene properties including bond length, chain twisting, aromaticity, and optical properties. Heavier chalcogenophenes are more quinoidal in character and consequently have reduced band gaps and larger degrees of planarity. We consider both the neutral and radical cationic species. Upon p-type doping, bond length rearrangement is indicative of a more delocalized electronic structure, which combined with optical calculations is consistent with the polaron-model of charge storage on conjugated polymer chains. A better understanding of the properties of these materials at their molecular levels will inevitably be useful in material design as the polymer community continues to explore more main group containing polymers to tackle issues in electronic devices.